Washing or dyeing with a non-terminal, vicinal alkanediol adduct of ethylene and propylene oxides

ABSTRACT

In the process of treating textiles which comprises contacting said textiles with an aqueous textile treating bath containing a wetting agent and recovering said treated textiles, the improvement which consists in utilizing from 0.1 to 5 gm/liter of a poorly foaming alkylene oxide adduct of from 5 to 20 mols of ethylene oxide and from 1 to 10 mols of propylene oxide in a mol ratio of 1:0.1 to 1 to a nonterminal, vicinal alkanediol having from 10 to 20 carbon atoms, as said wetting agent.

United States Patent 1191 Schade et a1.

[ WASHING OR DYEING WITH A NON-TERMINAL, VICINAL ALKANEDIOL ADDUCT OFETI-IYLENE AND PROPYLENE OXIDES [75] Inventors: Wolfgang Schade, Hilden;Peter Krings, Krefeld; Heimold Batka, Dusseldorf-Reisholz, all ofGermany [73] Assignee: Henkel & Cie, GmbH, Dusseldorf,

Germany 22 Filed: Dec. 13, 1972 21 Appl. No.: 314,688

52 US. Cl. 8/93; 8/137; 8/173 51 1m.c1 ..D06p1/68 58 Field of Search8/137, 93, 169

[56] References Cited UNITED STATES PATENTS 2,671,811 3/1954 Baird252/358 July 1, 1975 5/1954 DeGroote 252/358 OTHER PUBLICATIONS Chem. &Eng. News, l/30/1956, Vol. 34, No. 5, pages P-477-480.

Primary ExaminerDonald Levy Attorney, Agent, or Firml-lammond & LittellABSTRACT In the process of treating textiles which comprises contactingsaid textiles with an aqueous textile treating bath containing a wettingagent and recovering said treated textiles, the improvement whichconsists 7 Claims, No Drawings 1 WASHING OR DYEING WITH A NON-TERMINAL,VICINAL ALKANEDIOL ADDUCT OF ETI'IYLENE AND PROPYLENE OXIDES PRIOR ARTIn the many washing and wetting processes used in the treatment oftextiles, including dyeing, considerable foaming problems occur with theusual wetting and washing agents, which up to now could only be partlysolved by the addition of anti-foaming substances. Spots are frequentlyformed on the goods on separation of the anti-foaming agents. On theother hand, the addition of special poorly foaming non-ionic wetting andwashing agents has not hitherto led to the desired results since, whenthe foaming was sufficiently reduced, the wetting and washing action wasnot satisfactory.

OBJECTS OF THE INVENTION It is an object of the present invention toprovide a development in the process of treating textiles whichcomprises contacting said textiles with an aqueous textile treating bathcontaining a wetting agent and recovering said treated textiles, whereinthe improvement consists in utilizing from 0.1 to 5 gm/liter of a poorlyfoaming alkylene oxide adduct of from 5 to 20 mols of ethylene oxide andfrom 1 to mols of propylene oxide in a mol ratio of 1:0.1 to l to anon-terminal, vicinal alkanediol having from 10 to carbon atoms, as saidwetting agent.

It is a further object of the present invention to provide a poorlyfoaming wetting agent for textile treatment comprising an alkylene oxideadduct of from 5 to 20 mols of ethylene oxide and from 1 to 10 mols ofpropylene oxide in a mol ratio of 1:0.1 to l to a nonterminal, vicinalalkanediol having from 10 to 20 carbon atoms.

These and other objects of the invention will become apparent as thedescription thereof proceeds.

DESCRIPTION OF THE INVENTION According to the present invention there isprovided a method of carrying out textile treatment processes using anaqueous bath containing a wetting or washing agent, and wherein the saidwetting or washing agent is a poorly foaming alkylene oxide adduct offrom 5 to 20 mols of ethylene oxide and from 1 to 10 mols of propyleneoxide adducted to alkanediols containing 10 to 20 carbon atoms, thehydroxyl groups of which are substantially non-terminal and adjacent toone another, as the said wetting and washing agents. By non-terminal aremeant diols in which the adjacent hydroxyl groups are distributed almoststatistically over the whole alkyl chain.

More particularly, the present invention provides an improvement in theprocess of treating textiles which comprises contacting said textileswith an aqueous textile treating bath containing a wetting agent andrecovering said treated textiles, the said improvement consists inutilizing from 0.1 to 5 gm/liter of a poorly foaming alkylene oxideadduct of from 5 to 20 mols of ethylene oxide and from 1 to 10 mols ofpropylene oxide in a mol ratio of 1:0.1 to 1 to a non-terminal, vicinalalkanediol having from 10 to 20 carbon atoms, as said wetting agent.

The present invention is'further directed to a poorly foaming wettingagent for textile treatment comprising an alkylene oxide adduct of from5 to 20 mols of ethylene oxide and from 1 to 10 mols of propylene oxidein a mol ratio of 1:0.1 to 1 to a non-terminal, vicinal alkanediolhaving from 10 to 20 carbon atoms.

The starting materials for the preparation of the adducts are aliphaticdiols, usually alkanediols of 12 to 20 carbon atoms, with non-terminaland adjacent or vicinal hydroxyl groups. Such diols are prepared inknown way from linear aliphatic olefins with isomeric double bonds, forexample by epoxidation with per-acids or hydrogen peroxide and lowercarboxylic acids forming per-acids, and subsequent saponification of theepoxides. The products obtained are normally mixtures of various diols,the diol group being statistically distributed over the carbon chain.The amount of 1,2-diols in the mixture is very small.

The reaction of these non-terminal, vicinal alkanediols with thealkylene oxides is effected in known way in the presence of acid oralkaline catalysts, preferably using elevated temperatures andpressures. Firstly, the desired amount of ethylene oxide is added ontothe diol followed by the amount of propylene oxide. In practice, thereaction with ethylene oxide is preferably carried out in a two-stageprocess, in which 1 mol of a diol or diol mixture is first reacted with1 mol of ethylene oxide. After separating any unreacted diol, thefurther reaction with the desired amount of ethylene oxide is effected.Subsequent to the addition of the ethylene oxide, the further reactionwith propylene oxide is carried out in the usual way. In the reactionpreferably only one polyalkylene glycol chain is formed per diolmolecule, since substantially only the primary hydroxyl groups resultingfrom the first reaction stage react further with the alkylene oxides atsufficient speed.

Suitable products according to the present invention are in particularthose which contain from 5 to 10 mols of ethylene oxide and from 3 to 10mols of propylene oxide added onto the diol and in which the molaramounts of the ethylene oxide to propylene oxide added onto the diol arein the ratio of from 1:0.1-1, preferably from 1:0.3-1. Diols or diolmixtures having alkyl chain lengths of from 14 to 18 carbon atoms arepreferred as starting materials. Examples of suitable substances are theadducts of 5 mol of ethylene oxide and 3 mol of propylene oxide, or 7mol of ethylene oxide and 3 mol of propylene oxide or 7 mol of ethyleneoxide and 5 mol of propylene oxide to diols or diol mixtures of anaverage chain length of 15 to 17 carbon atoms.

The said products are marked by very little foaming and have a highwetting and washing action. These products may be utilized attemperatures ranging from about 25C to C while maintaining theproperties of non-foaming with excellent wetting and washingcapabilities.

The adducts described are very suitable as wetting and washing agents inmany processes of textile manufacture. For example, they are used forthe improvement of the penetration of finishing baths; in the sizing ofmaterial which contains difiiculty wettable waxes or preparations; aswetting agents in carbonizing liquors; for continuous scouring, dyeing,washing, desizing and bleaching processes, where they ensure safety andacceleration of the operations; in the pigment pad process of cotton onfoulard machines; for cross coil dyeing in a backwashing machine ofworsted tops; in prescouring and dyeing in high temperature reel dyeingmachines; in dyeing in high temperature apparatus; in nozzle washingmachines; for jig processes and so forth. In all such cases the productsare marked by extremely low foaming, so that the use of specialantifoaming agents is unnecessary. It is to be noted that the tendencyof the adducts to foam decreases still further as the temperature rises,so that the adducts of the present invention are particularly suitablefor use in baths which are operated at elevated temperatures.

The quantity of the products to be added to the baths depends upon theintended use and upon the desired results. In general, the amount addedis between about 0.1 and gm/liter, preferably between about 0.5 and 3gm/liter. For example, dyebaths require a concentrationn of about 1 to 3gm/liter; yarn washing liquors require a concentration of about 1 to 2gm/liter; sizing and finishing liquors require a concentration of about0.5 to 1 gm/liter and carbonizing liquors require a concentration ofabout 0.5 to 1.5 gm/liter. The baths have also a good stability athigher temperatures or with a higher concentration of electrolyte. Theadducts are 'normally soluble in water at low temperatures giving aclear solution; at higher temperatures above the socalled turbiditypoint the solutions become cloudy without, however, any separationoccurring. The superior wetting and washing properties are alsomaintained above the turbidity point, while the already minimal foamingtendency decreases practically to zero in this temperature region.

The following examples are merely illustrative of the present inventionwithout being deemed limitative in any manner thereof.

EXAMPLES The following Table contains data on important technicalapplication properties of the substances used according to the presentinvention as well as some commercial products for comparison. It can beobserved from the Table that the said products are practicallynon-foaming with excellent wetting and washing properties.

EXAMPLE 2 Cotton piece goods were padded on the foulard at a speed ofm/min. with 20 gm/liter of lndanthrene blue GCD (Registered Trade Mark)with addition of 3 gm/liter of an adduct of 77 mols of ethylene oxideand 5 mols of propylene oxide to a diol mixture of chain lengths 15 to18 carbon atoms. After intermediate drying the goods were vatted asusual with hydrogensulfite in alkaline liquor. The dyeing was developedwith steam and again scoured with the adduct of 5 mols of ethylene oxideand 3 mols of propylene oxide to a diol mixture of chain lengths 15 to18 carbon atoms.

Both the padding process and the further treatment stages proceededcompletely free from trouble, since practically no foaming occurs. Theresult of the dyeing was satisfactory.

EXAMPLE 3 lst Bath 2nd Bath gin/liter H 0 40C 0.5 0.5 ml/liter aceticacid 60% Technical application properties of the substances according tothe invention as well as of some comparative products.

Wetting action acc. to DIN 53901 (wetting times in Product Washingaction in brightening with 1 gm/l of Foaming test with lg/l ofsurface-active sec.) surface-active product product at 60"C. 0.5 gm/l1.0 gm/l 1.5 gm/l Wool Cotton Diolen Beating In the at at at methodcross coil 30C 90C 40C acc. to dyeing Bath Bath Bath DIN 53902 machineratio ratio ratio ml foam cm. foam 'roducts according to he invention:In; diol 5E0 3P0 84 34 12 80 51 0 0 I diol 7E0 3P0 72 71 1O 67 65 53 0 0I, diol 7E0 5P0 79 21 9 36 59 42 O O Iommercial surface-active ompoundsas products for omparison: lecyl alcohol 3E0 78 21 8 45 50 29 20 10.,,;-fatty alcohol lOEO 143 72 47 66 60 250 foams over 30 cm)lonylphenol 9E0 93 32 13 71 75 72 200 foams over 30 cm) EXAMPLE 1 3rdBath C 2 gxrlI/liter of the adduct from 5 mols of ethy ene oxide and 3mols of re lene Cross-wound bobbins of cotton were boiled for 30 oxideto an alkanediol miXtUl': hzii/ in from 15 to 18 carbon atoms un. at 95with 1 gm/hter of the adduct of 7 molsof 4th Bath water M .hylene oxideand 3 mols of propylene oxide to a dlol 5th Bath 25"C Water Thefine-pored stable foam occurring during use of commercial washing agentswas completely lacking in this case. The plant ran for several days freefrom trouble when the above-mentioned poorly foaming adduct was used.The cleaning result was satisfactory.

Although the present invention has been disclosed in connection with afew preferred embodiments thereof, variations and modifications may beresorted to by those skilled in the art without departing from theprinciples of the new invention. All of these variations andmodifications are considered to be within the true spirit and scope ofthe present invention as disclosed in the foregoing description anddefined by the appended claims.

We claim:

1. In the process of treating textiles which comprises contacting saidtextiles with an aqueous textile treating bath containing a wettingagent and recovering said treated textiles, the improvement whichconsists in utilizing from 0.1 to 5 gm/liter of a poorly foamingalkylene oxide adduct of from 5 to 20 mols of ethylene oxide and from 1to mols of propylene oxide in a mol ratio of I 20.1 to l to anonterminal, vininal alkanediol having from 10 to carbon atoms, as saidwetting agent.

2. The process as claimed in claim 1, in which the adduct is from 5 to10 mols of ethylene oxide and from 3 to 10 mols of propylene oxideadducted to said alkanediol having from 14 to 18 carbon atoms.

3. The process as claimed in claim 1, in which the diol adduct has amolar ratio of ethylene oxide to propylene oxide of from 1:0.3 to 1:1.

4. The process as claimed in claim 1, in which the aqueous bath containsfrom about 0.5 to 3 gm/liter of solution of said poorly foaming adduct.

5. The process as claimed in claim 1, in which said poorly foamingadduct is selected from the group consisting of the adducts of 5 mols ofethylene oxide and 3 mols of propylene oxide to an alkanediol oralkanediol mixture of 15 to 17 carbon atoms, the adducts of 7 mols ofethylene oxide and 3 mols of propylene oxide to an alkanediol oralkanediol mixture of 15 to 17 carbon atoms, and the adducts of 7 molsof ethylene oxide and 5 mols of propylene oxide to alkanediols oralkanediol mixtures of 15 to 17 carbon atoms.

6. The process as claimed in claim 1, in which said poorly foamingadduct is selected from the group consisting of the adducts of 5 mols ofethylene oxide and 3 mols of propylene oxide to a hexadecanediol, theadducts of 7 mols of ethylene oxide and 3 mols of propylene oxide to ahexadecanediol, and the adducts of 7 mols of ethylene oxide and 5 molsof propylene oxide to a hexadecanediol.

7. The process as claimed in claim 1, in which said poorly foamingadduct is selected from the group consisting of the adducts of 7 mols ofethylene oxide and 3 mols of propylene oxide to an alkanediol mixture of15 to 18 carbon atoms, the adducts of 7 mols of ethylene oxide and 5mols of propylene oxide to an alkanediol mixture of 15 to 18 carbonatoms and the adducts of 5 mols of ethylene oxide and 3 mols ofpropylene oxide to an alkanediol mixture of 15 to 18 carbon atoms.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTIGN Patent No. 9 5Dated July 1, 1975 I Wolfgang Sohade et al.

It is certified that error appears in the above-identified patent andthat said Letters Patent are hereby corrected as shown below:

On the Cover Sheet, the following should be added:

Foreign Application Priority Data Dec. 17, 1971 Germany --2l626'72Column line 18, "'77 mole" should read '7 mols Signed and fieaicd this Attes t:

RUTH C. MASON C. MARSHALL DANN Arresting Ofl'icer (mnmissiunvrnj'lar..=ms and Trademarks

1. IN THE PROCESS OF TREATING TEXTILES WHICH COMPRISES CONTACTING SAIDTEXTILES WITH AN AQUEOUS TEXTILE TREATING BATH CONTAINING A WETTINGAGENT AND RECOVERING SAID TREATED TEXTILES, THE IMPROVEMENT WHICHCONSISTS IN UTILIZING FROM 0.1 TO 5 GM/LITER OF A POORLY FOAMINGALKYLENE OXIDE ADDUCT OF FROM 5 TO 20 MOLS OF ETHYLENE OXIDE AND FROM 1TO 10 MOLS OF PROPYLENE OXIDE IN A MOL RATIO OF 1:0 TO 1 TO ANONTERMINAL, VINIAL ALKANEDIOL HAVING FROM 10 TO 20 CARBON ATOMS, ASSAID WETTING AGENT.
 2. The process as claimed in claim 1, in which theadduct is from 5 to 10 mols of ethylene oxide and from 3 to 10 mols ofpropylene oxide adducted to said alkanediol having from 14 to 18 carbonatoms.
 3. The process as claimed in claim 1, in which the diol adducthas a molar ratio of ethylene oxide to propylene oxide of from 1: 0.3 to1:1.
 4. The process as claimed in claim 1, in which the aqueous bathcontains from about 0.5 to 3 gm/liter of solution of said poorly foamingadduct.
 5. The process as claimed in claim 1, in which said poorlyfoaming adduct is selected from the group consisting of the adducts of 5mols of ethylene oxide and 3 mols of propylene oxide to an alkanediol oralkanediol mixture of 15 to 17 carbon atoms, the adducts of 7 mols ofethylene oxide and 3 mols of propylene oxide to an alkanediol oralkanediol mixture of 15 to 17 carbon atoms, and the adducts of 7 molsof ethylene oxide and 5 mols of propylene oxide to alkanediols oralkanediol mixtures of 15 to 17 carbon atoms.
 6. The process as claimedin claim 1, in which said poorly foaming adduct is selected from thegroup consisting of the adducts of 5 mols of ethylene oxide and 3 molsof propylene oxide to a hexadecanediol, the adducts of 7 mols ofethylene oxide and 3 mols of propylene oxide to a hexadecanediol, andthe adducts of 7 mols of ethylene oxide and 5 mols of propylene oxide toa hexadecanediol.
 7. The process as claimed in claim 1, in which saidpoorly foaming adduct is selected from the group consisting of theadducts of 7 mols of ethylene oxide and 3 mols of propylene oxide to analkanediol mixture of 15 to 18 carbon atoms, the adducts of 7 mols ofethylene oxide and 5 mols of propylene oxide to an alkanediol mixture of15 to 18 carbon atoms and the adducts of 5 mols of ethylene oxide and 3mols of propylene oxide to an alkanediol mixture of 15 to 18 carbonatoms.